Triazine derivatives as antioxidants

ABSTRACT

New 2,4 bis-(3,5-di-tert.butyl-4-hydroxy-phenoxy)-s-triazines are stabilizers for organic materials. They are prepared by reacting the bis-(imino-carbonic acid-(3,5-di-tert.butyl-4hydroxyphenyl)ester)-imide with a corresponding carboxylic acid chloride.

United States Patent. 1191 3 1111 3,867,337 Brunetti 1 1 Feb. 18, 1975 TRIAZINE DERIVATIVES AS ANTIOXIDANTS [56] References Cited [75] Inventor: Heimo Brunetti, Reinach, UNITED STATES PATENTS Switz rland 1,897,428 2/1933 Hentrich ct =11 200/2411 2,762,797 9/1956 Hcchenblcikner v 1 260/248 [73] Assgnee' g' Cmpmamn Ardsley 3,530,127 9/1970 Bilzmd cl 111 260/248 3,706,740 12/1972 Dexter ct ill. 260/148 22 il Man 15 1973 3,709,883 [/1973 Dexter ct ul. 260/248 [21] Appl 341639 Primary Examiner-Donald E. Czujn R l t d Us. A li ti D t Assistant E.raminerR. A. White [62] Division of Ser. No. 192,592, Oct. 26, 1971. Pat. No.

3,775,411. [57] ABSTRACT New 2,4 bis-(3,5-di-tert.butyl-4-hydr0xy-phenoxyl-s- [30] Forelgn Apphcatmn Pnorlty Data triazines are stabilizers for organic materials. They are Nov. 9, 1970 Switzerland 16548/70 prepared by reacting the bis-[imino-carbonic acid- (3,5-ditert.butyl-4-hydroxyphenyl)esterl-imide with a 5- 5 5360/ C corresponding carboxylic acid chloride. [51] Int. Cl. C08f 45/60, C08g 51/60 5 Cl N D [58] Field of Search 260/458 NT, 248 cs CROSS-REFERENCE TO RELATED CASES This application is a division of my application, Ser. No. 192,592, filed Oct. 26, 1971, now US. Pat. No. 3,775,411, issued Nov. 27, 1973.

The present invention relates to new compounds, the method for their manufacture, their use for stabilising organic material against thermo-oxidative degradation and, as an industrial product, the organic material stabilised with their aid.

It has been found, surprisingly, that new compounds of the formula I in which R denotes hydrogen, alkyl with 1 to 17 carbon atoms, alkenyl with 2 to 4 carbon atoms, thiaalkyl with 3 to carbon atoms, cyclohexyl, benzyl, alkylene with 4 to 8 carbon atoms or the radical R denotes methyl or ethyl and m and n denote l or 2, are very suitable for stabilising organic material against thermo-oxidative degradation.

Herein, the new compounds surprisingly show a better activity than the compounds previously known from Belgian Patent Specification No. 718,962, in which R, denotes an aryl group.

The new compounds of the formula I can be manufactured if a compound of the formula II c cn ca c 2 1 {T E CH3 1 oc c 0 on 013 \N/ ,cu

c ,c ea or R2 3 3 R2 is reacted with a compound of the formula III R, (COCI),l

(ill) in which formulae II and III R,, R and n have the abovementioned meaning, in the presence of a base, and if n denotes 1, approximately molar amounts of the compound of the formula ll are reacted or, if n denotes 2, approximately double the molar amounts of the compound ll are reacted, relative to the compound of the formula Ill. 7

A tertiary amine, such as triethylaminc, can for example be used as the base. The reaction is advantageously carried out in a solvent, for example hexane, toluene, ether or acetone.

Compounds of the formula I, in which R, denotes hydrogen can be manufactured by reaction of a compound of the formula II with orthoformic acid triethyl ester.

The compounds of the formula I can also be obtained in a manner which is in itself known, by reaction of a compound of the formula IV Cl- R N with approximately 2 n mols of a compound of the formula V H H i 3 on f 3 R C---R l H CH (V 3 in which formulae R,, R and n are defined as under formula I, in the presence of a base.

In the formula l, R, for example denotes an alkyl group with l to 17 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, heptyl, iso-heptyl, nonyl, undecyl, pentadecyl or heptadecyl, an alkenyl group with 2 to 4 carbon atoms such as vinyl or 2-butenyl, a thiaalkyl group with 3 to 20 carbon atoms such as the methyl-, ethyl-, butyl-, octyl-, tert.-octyl-, dodecyl-, tert.- dodecylor octadecyl-thioethyl group or the butyl-, octyl-, dodecylor octadecyl-thiomethyl group or an alkylene group with 4 to 8 carbon atoms, such as the tetramethylene, hexamethylene or octamethylene group.

Preferred compounds of the formula I are those in which R, denotes an alkyl group with 7 to 17 carbon atoms, a cyclohexyl group, a benzyl group, a thiaalkyl group with 5 to 14 carbon atoms, an alkylene group with 4 to 8 carbon atoms or the radicals thio-bis-(4-methyl-6-tert.-butylphenol),

--CH OH and CH CH on The compounds according to the invention protect organic materials, especially organic polymers, against thermo-oxidative degradation. Amongst the polymers which are protected by the compounds according to the invention there should be mentioned: polyolefines, preferably a-olefine polymers, such as polypropylene, optionally crosslinked polyethylene, polyisobutylene, polymethylbutenel, polymethylpentene-l, polybutene-l polyisoprene and polybutadiene; copolymers of the monomers on which the homopolymers mentioned are based, such as ethylene-propylene copolymers, propylenebutene-lcopolymers, propylene-isobutylene copolymers, styrenebutadiene copolymers, and terpolymers of ethylene and propylene with a diene, for example hexadiene, dicyclopentadiene or ethylidenenorbornene; mixtures of the abovementioned homopolymers, for example mixtures of polypropylene and polyethylene, polypropylene and polybutene-l, and polypropylene and polyisobutylene. Polypropylene, as well as its mixtures and the copolymers which contain propylene units, are at the same time preferred.

Further polyaddition compounds, such as copolymers and graft polymers of styrene and butadiene with acrylonitrile, acrylic and methacrylic acid esters and optionally with vinyl esters and vinyl chloride, or natural polymers, such as rubber, and polycondensation products such as polycarbonate, polyamides, polyesters, polyacetals and polyurethanes. High molecular monomeric substances, such as hydrocarbons, for example mineral oils; esters, for example animal or vegetable fats, oils or waxes, or oils and waxes based on synthetic esters.

The compounds of the formula I are incorporated 4 into the substrates at a concentration of 0.01 to by weight, calculated relative to the material to be stabilised. Preferably, 0.05 to 1.5, and particularly preferably 0.1 to 0.8, by weight of the compounds, calculated relative to the material to be stabilised, are incorporated into the latter.

The incorporation into polymers can take place before or after polymerisation, or before or after shaping, for example by mixing the compounds of the formula l, and optionally further additives, into the melt or solution of the polymers in accordance with the methods customary in the art. It can also be effected by applying the dissolved or dispersed compounds to the polymer, where necessary with subsequent evaporation of the solvent.

As further additives together with which the compounds according to the invention can be employed, there may be mentioned:

1. Antioxidants of the aminoaryl and hydroxyaryl series. Amongst the latter, the sterically hindered phenol compounds should be mentioned, for example: 2,2- 4,4'-thio-bis- (3-methyl-6-tert.-butylphenol), 2,2'-methylene-bis-(4- methyl-6-te rt.-butylphenol 2,2 -methylene-bis-4- ethyl-6-tert.-butylphenol), -methylene-bis-(2-methyl- 6-tert.-butylphenol), 4,4'-butylidene-bis-(3-methyl-6- tert.-butylphenol), 2,2-methylene-bis-[4-methyl-6-(amethylcyclohexyl)-phenol], 2,6-di-(2-hydroxy-3-tert.-

4 butyl-S-methylbenzyl)-4-methyl-phenol, 2,6-di-tert.- butyl-4-methylphenol, 1,1 ,3-tris-2-methyl-(4-hydroxy- S-terL-butylphenyl)-butane, l,3,5-trimethyl-2,4,6-tri- (3,5-di-tert.-butyl-4-hydroxy-benzyl)-benzene, esters of B-4-hydroxy-3,5-di-tert.-butylphenyl-prop'ionic acid with monohydric or polyhydric alcohols, such as methanol, ethanol, octadecanol, hexanediol, nonanediol, thiodiethylene glycol, trimethylhexanediol, trimethylolethane or pentaerythritol, 2,4-bis-octylmercapto-6- (4-hydroxy-3,5-di-tert.-butylanilino)-s-triazine. 2,4- bis-(4-hydroxy-3,5-di-tert.-butylphenoxy)-6- octylmercapto-s-triazine, l,l-bis-(4-hydroxy-2-mcthyl- 5-tert.-butyl-phenyl)-3-dodecyl-mercapto-butane, 4- hydroxy-3,S-di-tert.-butylbenzyl-phosphonic acid esters, such as the dimethyl, diethyl or dioctadecyl ester, (3-methyl-4-hydroxy-5-tert.-butylbenzyl)-malonic acid dioctadecyl ester, S-(3,5-dimethyl-4-hydroxybcnzyl)- thioglycollic acid octadecyl ester, and esters of his- (3,5-di-tert.-butyl-4-hydroxybenzyl)-malonic acid such as the didodecyl ester, the dioctadecyl ester and the 2-dodecylmercaptoethyl ester.

Amongst the aminoaryl derivatives, aniline and naphthylamine derivatives as well as their heterocyclic derivatives should be mentioned, for example phenyl-lnaphthylamine, phenyl-Z-naphthylamine, N,N-diphenyl-p-phenylenediamine, N,N-di-2-naphthyl-pphenylenediamine, N,N'-di-sec.butyl-pphenylenediamine, 6-ethoxy-2,2,4-trimethyl-l ,2- dihydroquinoline, 6-dodecyl2,2,4-trimethyll ,2- dihydroquinoline, monooctyliminodibenzyl and dioctyliminodibenzyl and polymerised 2,2,4-trimethyl-l,2- dihydroquinoline, though in the case of the combined use of the compounds according to the invention with the abovementioned amine compounds the stabilised polymer has less good colour properties because of the tendency to discolouration of the amine compounds.

2. UV-Absorbers and light protection agents, such as:

a. 2-(2'-Hydroxyphenyl)-benztriazoles, for example the 5-methyl, 3',5-di-tert.butyl, 5'-tert.butyl, 5- chloro-3',5'-di-tert.-butyl, 5-chloro-3"tert.butyl- 5'-methyl, 3',5'-di-tert.amyl, 3'-methyl-5-B-carbomethoxyethyl and 5-chloro-3,5'-di-tert.amyl derivative.

b. 2,4-Bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines, for

example the 6-ethyl or 6-undecyl derivative.

c. 2-Hydroxy-benzophenones, for example the 4- hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4- dodecyloxy, 4,2',4-tri-hydroxy or 2'-hydroxy-4,4'- dimethoxy derivative.

d. l,3-Bis-(2'-hydroxy-benzoyl)-benzenes, for example l,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl benzene, l,3-bis-(2-hydroxy-4'-octoxy-benzoyl)- benzene and l,3-bis-(2'-hydroxy-4-dodecyloxybenzoyl)-benzene.

e. Aryl esters of optionally substituted benzoic acids,

for example phenyl salicylate, octylphenylsalicylate, benzoylresoreinol, dibenzoylresorcinol, 3,5- di-tert.butyl-4-hydroxybenzoic acid 2,4-di-tert.butyl-phenyl ester or octadecyl ester.

f. Acrylates, for example a-cyano-B,[3-

diphenylacrylic acid ethyl ester or isooctyl ester, a-carbomoethoxy-cinnamic acid methyl ester, a-cyano-B-methyl-p-methoxy-cinnamic acid methyl ester and butyl ester and N-(B-carbomethoxyvinyl)-2-methyl-indoline.

g. Nickel compounds, for example nickel complexes of 2,2'-thiobis-(4-tert.octylphenol), such as the lzland 1:2-c0mplex, optionally with other ligands such as n-butylamine, nickel complexes of bis-(4- tertoctylphenyl)-sulph0ne, such as the 2:1- complcx, optionally with other ligands such as 2- ethylcaproic acid, nickel dibutyldithiocarbamate, nickel salts or 4-hydroxy-3,5-di-tert.butylbenzylphosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, or the nickel complex of 2-hydroxy-4methyl-phenylundecylketonoxime.

h. Oxalic acid diamides, for example 4,4-dioctyloxy-oxanilide, 2,2-di-octyloxy-5,5'-di-tert.- butyl-oxanilide and 2,2'-di-dodecyloxy-5,5-ditert.-butyl-oxanilide.

3. Phosphites, such as triphenylphosphite, diphenylalkylphosphites, phenyldialkylphosphites, trinonylphenylphosphites, trilaurylphosphite, trioctadecylphosphite, 3,9-di-isodecyloxy-2,4,8,l0-tetraoxa-3,9- diphosphaspiro-(5,5)-undecane and tri-(4-hydroxy- 3,5-di-tert.butylphenyl)-phosphite.

4. Nucleating agents, such as 4-tert.butylbenzoic acid, adipic acid and diphenylacetic acid.

5. Compounds which destroy peroxides, such as esters of ,B-thiopropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester.

Salts of 2-mercaptobcnzimidazole, for example the zinc salt, and diphenylthiourea.

6. Metal deactivators, such as oxanilide, dicarboxylic acid dihydrazides, dicarboxylic acid bisphenylhydrazides, salicylic acid hydrazide, N- salicyloyl-N-salicylidenehydrazine, bis-salicyloyldicarboxylic acid dihydrazides, bis-acylated dicarboxylic acid dihydrazides and salicyloylhydrazinotriazines.

7. Other additives such as antistatic agents, flameproofmg agents, asbestos, glass fibres, kaolin, talc, blowing agents, carbon black, plasticisers, dyeing auxiliaries, dyestuffs, pigments, vulcanisation acelerators and other chemicals customarily used in the rubber industry, agents for lowering the pour point, corrosion protection agents and rust protection agents, dispersing 40 agents and anti-foaming agents.

The invention is explained in more detail in the examples which follow. in the formulae of the examples denotes tertiary-butyl.

EXAMPLE 1 Manufacture of the Compounds of the Formula 1 Stage I l 11 g of 3,5-di-tert.butyl-4-hydroxyphenyl-cyanate are first introduced into 500 ml of hexane. Ammonia gas is passed over the surface of the stirred solution, at

5C, until the precipitate which has formed no longer increases. The bis-[imino-carbonic acid-(3,5-ditert.butyl-4-hydroxyphenyl)-ester]-imide is filtered off and dried in vacuo. 128 g of melting point l88l90C (Kofler bench) are thus obtained.

Stage 2 10.2 g of bis-[imino-carbonic acid-(3,5-di-tert.butyl- 4-hydroxyphenyl)-ester]-imide are suspended in ml of toluene. 4.8 g of lauric acid chloride are added dropwise at O5C over the course of 15 minutes, followed by 2.2 of triethylamine added dropwise. The temperature is raised to C and maintained thereat for 1 hour, the mixture is filtered, the residue is washed with toluene, and the entire filtrate is evaporated in vacuo. The residue is dissolved in petroleum ether. On cooling the solution to -0C, the product crystallises out. It is filtered off, rinsed with cold petroleum ether and recrystallised from hexane. 10.5 g of 2,4-bis-(3.5-ditert.butyl4-hydroxy-phenoxy)-6-undecyl-s-triazine (Stabiliser No. 8) of melting point 58-60C are thus obtained.

If the lauric acid chloride in the preceding example is replaced by an equivalent amount of the corresponding acid chloride, the stabilisers indicated in Table l are obtained under the same reaction conditions. Working up has to be varied slightly from case to case. and this is recorded very briefly in the table.

Stabiliser No. l was obtained if, in the above method of manufacture, the lauric acid chloride was replaced by an excess amount of orthoformic acid triethyl ester and the triethylamine was omitted.

Table I Stabili- I-Telfing ser No. X Working up P l H Recrystallised from hexane C o 2 -(1Il Reerystallised from hexane 186 C O 3 -C H Recrystallised. from ligroin C O 4 -C H Recrystallised from ligroin C -0" 5 C li Recrystallised from ligroin 9 v en on v I 3 3 o 6 -CH -CHCH C-CH Recrystallised from ligroin 207 C .0 7 -C lI Chromatographed (toluene/silica gel) N 50 C Continuation of Table I Stabili- Melti c ser No. X P Working up 1 9 -C H F Chromatographed (toluene/silica gel) and recrystal- 50C lised from acetonitrile 10 -CH CH Recrystallised from ligroin 19 11 Recrystallised from methanol/water 5 12 4213 0 Recrystallieed from iaopropanol 165C l3 wa s-0 x1 3 Recrystallised from hexane 172C 14- -G C S0 H Recrystallised from hexane 13 15 cn cn -s-c H -(n) I Chromatographed (toluene/silica gel) 98C 16 CH -S-C H (tert.) f Chromatographed (toluene/silica. gel) 63- 5 17 -CH CH -S-C H Chromatographed (toluene/silica gel) 113 18 -GH CH -S-t' H Recrystallieed from acetonitrile (cooling with CO Below 2 2 l 37 2 room temperature (oil) 9 413 -6-0 Reerystallised from ligroin 226C 20 2 26. Recrystallised from ligroin 1 5 21 -(0H Recrystallieed from toluene 206C 22 I Recrystallised from ligroin 157 (Note on Tlbll I) n In this can, 1 mol of imide was reacted with 11101 or dioarboxylio acid chloride and 1 mol of triethylamine.

Analogously, reaction of bis-[imino-carbonic acid- (3,5-di-tert.amyl-4-hydroxyphenyl)-ester]-imide with cyclohexane-carboxylic acid chloride yields 2,4-bis- (3,5-di-tert.-amyl-4-hydroxy-phenoxy)-6-cyclohexyl-striazine of melting point l43l44C.

In the use examples, the following two compounds from Belgian Patent No. 718,962 were also tested, for

comparison:

EXAMPLE 2 Stabilisation of polypropylene (1 mm sheets) a. Manufacture of the Test Specimens parts of polypropylene (melt index 3.2) are kneaded in a Brabender plastograph for 10 minutes at 200C with the stabilisers listed in Tables 2 and 3 below. This ensures homogeneous distribution of the stabilisers. The composition thus obtained is subsequently pressed in a platen press at 260C platen temperature to give 1 mm thick sheets from which strips 1 cm wide and 17 cm long are punched. b. Test The effectiveness of the stabilisers added to the test sheets is tested by heat ageing the sheets in a circulating air oven at and 149C. The incipient visible decomposition of the test specimen is regarded as the end point. For results, see Tables 2 and 3.

Table 2 Continued Table 5 Comparisomfrom Belgian Patent 140. 718.962

0.1 23 0.3 DLTDP 163 37 DLTDP" Dilaurylthiodipropionalc EXAMPLE 3 Stabilisation of Polypropylene 1. chips) Shavings (chips) of 25 1 thickness are cut from the 1 mm thick test sheets described in Example 2, with the aid of a microtome. These chips are clamped between grids of stainless steel and the sample carriers thus obtained are suspended in a circulating air oven and subjected to ageing at 135 or 147C. The time after which, on lightly tapping the grids, degraded polypropylene drops out in a powdered form (checked 12 X daily) is taken as the end point.

For results, see Tables 4 and 5.

Comparison, from Belgian Patent No. 718,962

Stabiliser No. Time up to decomposition, in days Compound No. Time u to decom 5M0. in hours At C At 149C At 135C At 147C H Comparison. from Belgian Patent 146718.962 5 0 1 9;, 5 0 DLTDP: 380 36 0.2 23 141 21 0.1% 7 0.3 DLTDP 672 96 0.1 8 0.3 DLTDP 672 Table 3 M 10 0.1 11 0.3 DLTDP 330 96 l 0.1 12 0.3 DLTDP 380 96 Compound No. Time up to decomposition, in days 0.1 13 0.3 DLTDP 430 I40 0.1 16 6.3 DLTDP 380 95 0.1 9 (13 DLTDP 178 40 15 0.1 17 0.3 DLTDP 280 70 l 20 +03 DLTDP 172 45 0.1 19 0.3 DLTDP 450 0.1 21 0.3 DLTDP 167 39 Comparison, from Belgian Patent No. 718,962

0.1 22 0.3 DLTDP 167 44 20 011 24 0.3 DLTDP 275 65 DLTDP Dilaurylthiodlpropionale I claim:

1. A composition of matter comprising an organic polymer and, in an amount of 0.01 to 5% by weight, a compound of formula I in which R, denotes thiaalkyl with 3 to 20 carbon atoms, alkylene with 4 to 8 carbon atoms or the radical R denotes methyl or ethyl and m and n denote 1 or 2. 2. A composition of matter according to claim 1, wherein said R is thiaalkyl with 5 to 14 carbon atoms. 3. A composition of matter according to claim 1 wherein said polymer is a polyolefin.

4. A composition of matter according to claim 3, wherein said polyolefin is polypropylene.

5. A composition of matter according to claim 1, wherein said compound is present in an amount of 0.05 to 1.5% by weight. 

1. A COMPOSITION OF MATTER COMPRISING AN ORGANIC POLYMER AND, IN AN AMOUNT OF 0.01 TO 5% BY WEIGHT, A COMPOUND OF FORMULA 1
 2. A composition of matter according to claim 1, wherein said R1 is thiaalkyl with 5 to 14 carbon atoms.
 3. A composition of matter according to claim 1 wherein said polymer is a polyolefin.
 4. A composition of matter according to claim 3, wherein said polyolefin is polypropylene.
 5. A composition of matter according to claim 1, wherein said compound is present in an amount of 0.05 to 1.5% by weight. 